Fuel 87 (2008) 29612966

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Biodiesel production from waste tallow

Haq Nawaz Bhatti a,*, Muhammad Asif Hanif a, Mohammad Qasim a, Ata-ur-Rehman b
a b

Department of Chemistry, University of Agriculture, Faisalabad 380400, Pakistan Oil Technology Laboratory, Ayub Agricultural Research Institute (AARI), Jhang Road, Faisalabad, Pakistan

a r t i c l e

i n f o

a b s t r a c t
In the present investigation an attempt has been made to use waste tallow as low cost sustainable potential feed stock for biodiesel production. Effect of various process parameters such as amount of catalyst, temperature and time on biodiesel production was investigated. The optimal conditions for processing 5 g of tallow were: temperature, 50 and 60 C; oil/methanol molar ratio 1:30 and 1:30, amount of H2SO4, 1.25 and 2.5 g for chicken and mutton tallow, respectively. Under optimal conditions, chicken and mutton fat methyl esters formation of 99.01 0.71% and 93.21 5.07%, was obtained after 24 h in the presence of acid. The evaluation of transesterication process was followed by gas chromatographic analysis of tallow fatty acid esters. A total of 98.29% and 97.25% fatty acids were identied in chicken and mutton fats, respectively. Both fats were found highly suitable to produce biodiesel with recommended fuel properties. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 3 October 2007 Received in revised form 19 April 2008 Accepted 22 April 2008 Available online 19 May 2008 Keywords: Biodiesel Tallow Acid catalysis Base catalysis Methanolysis

1. Introduction Biodiesel, an alternative fuel, is derived from the fats of animals and plants. As energy demands increase and fossil fuels are limited, research is directed towards alternative renewable fuels [12]. The main advantages of using this alternative fuel are its renewability, biodegrability and better quality exhaust gases [3]. Fatty acid methyl esters (FAME) from vegetable and animal fats have shown promise as biodiesel, due to improved viscosity, volatility and combustion behavior relative to triglycerides, and can be used in conventional diesel engines without signicant modications [49]. Biodiesel has higher oxygen content than petroleum diesel and its use in diesel engines have shown great reduction in emission of particulate matter, carbon monoxide, sulfur, polyaromatics, hydrocarbons, smoke and noise [1011]. In addition, burning of vegetable-oil based fuel does not contribute to net atmospheric CO2 level because such fuel is made from agricultural materials which are produced via photosynthetic carbon xation. The substitution of conventional diesel fuels with fatty acid methyl esters already comprises a commercial activity in many countries of world [1213]. However, the use of biodiesel has not expanded into developing countries, due to the higher prices than conventional diesel. The higher cost of biodiesel is due to its production mostly from expensive high-quality virgin oil. Use of low-cost feedstock such as waste frying oils and non-edible oils in an acid-catalyzed process should help to make biodiesel competitive in price with petroleum diesel [1415]. The most common way to produce bio* Corresponding author. Fax: +92 41 9200764. E-mail address: hnbhatti2005@yahoo.com (H.N. Bhatti). 0016-2361/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2008.04.016

diesel is by transesterication, which refers to a catalyzed chemical reaction involving vegetable oil and an alcohol to yield fatty acid alkyl esters (i.e., biodiesel) and glycerol [16]. Transesterication reactions can be alkali-catalyzed, acid-catalyzed or enzyme-catalyzed. The rst two types have received the greatest attention and are the focus of this article [1718]. Tallow is the animal fat and its use is declined due to changing feeding habits of people and the soap industry cannot take up all the excess animal fat produced. It can be used for the production of biodiesel and other oleochemicals. Therefore, the present project was undertaken to carefully evaluate the biodiesel production potential of chicken and mutton tallow. The main objective of the present research was to assess the acid and base catalyzed processes to produce biodiesel using waste chicken and mutton tallow.

2. Experimental 2.1. Materials Waste chicken and mutton fats were collected form City Slaughter House of Faisalabad, Pakistan. Fats were melted by slowly heating up to 60 C (under reduced pressure to avoid any degradation) to remove the waxy materials and other suspended matters and residues. Melted fats were then ltered, centrifuged and decanted. The processed chicken and mutton tallow were homogeneous in nature, which were stored in air tight opaque plastic jars to prevent oxidation. All the analytical grade reagents including sodium thiosulphate, sodium hydroxide, hydrochloric

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acid, sulphuric acid and methanol were purchased from Fluka chemicals. 2.2. Transesterication Transesterication of chicken and mutton fats was carried out under different experimental conditions by using acid and base catalysis for the production of fatty acid methyl esters. 2.2.1. Acid catalyzed transesterication Three levels of concentrated sulfuric acid catalyst (25%, 50% and 100% of fat) at four different temperatures (30, 40, 50 and 60 C) were employed to transesterify chicken and mutton fats at uniform shaking (130 rpm). Tallow (5 g) and methanol (150 mL) were taken in 250 mL asks for all experiments. The reaction mixture was heated for specied period of time, cooled and distilled to remove excess methanol. Glycerol and methyl esters (biodiesel) were the main components of the obtained mixture. The mixture was separated into two layers using a separating funnel. The upper oil layer (biodiesel) was separated and washed with hot water (50 C) until the washing was neutral. Biodiesel yield (wt.%) relative to the weight of tallow was estimated. 2.2.2. Base catalyzed transesterication Base catalyzed transesterication was carried out using three different methods. In rst method, to 120 g melted tallow, 1.8 g KOH dissolved in 33.5 mL methanol were added at constant stirring for 1 h at 30 C, the mixture was transferred to a separatory funnel and glycerol was allowed to separate for a minimum of 3 h. After draining off the glycerol, methyl ester was washed twice with 1:1 volume of water for 1 h to remove excess methanol [18]. In second method, to 120 g melted tallow, 2.5 g KOH dissolved in 24 mL methanol was added at constant stirring for 1 h at room temperature, the mixture was transferred to a separatory funnel and glycerol was allowed to separate for a minimum of 3 h. After draining off the glycerol, methyl ester was washed twice with 1:1 volume of water for 1 h to remove excess methanol [19]. In third method 50 g tallow was taken in 250 mL conical ask equipped with magnetic stirrer. Potassium hydroxide (1% of fats weight) dissolved in methanol (22.5% of tallows weight) was added to ask. Stirring was continued for 2 h at room temperature, the mixture was transferred to a separatory funnel and glycerol was allowed to separate and washed up to one week [12]. 2.3. Biodiesel evaluation The properties of methyl esters were determined by methods specied in Handbook of analytical methods for fatty acid methyl esters as diesel substitute [11] or by equivalent standard methods.

Acid value, viscosity, density, iodine value, saponication value, moisture content and ash contents were determined according to ISO 660, 3104, 3675, 3961, 3657, 662 and 6884, respectively. Cloud point and pour point were measured using ISO 3016 and ISO 3015, respectively, and iodine value using ISO 3961. Fatty acid compositions of biodiesel were determined by gas chromatography. Cetane number (CN) of biodiesel was empirically determined according to the method described by Krisnangkura, 1986 [20]. Each fraction of oil was analyzed to determine triglycerides in term of determining fatty acid components. A 100 lL of the test sample was thoroughly mixed with 1 mL of n-hexane and 1 lL of sodium methoxide in a 2 mL vial, and then shaken vigorously. The clear upper layer of methyl ester was pipetted off and injected into a GC column (methyl lignoserate coated (lm thickness 0.25 lm) SP-2330 polar capillary column (30 m 0.32 mm; Supelco Inc., Supelco Park Bellefonte, PA). A gas chromatograph (Model, G-3000, HITACHI) was used to determine the fatty acids prole. The oven temperature was set at 190 C, the detector (FID) and injector temperature held constant at 250 C. Carrier gas ow rate was 1 mL/min with a split ratio of 1:100. Chromato-integrator (HITACHI, D-2500) and an auto injector (Al-1000) were used. 2.4. Statistical analysis All the experiments were conducted in triplicate and data are reported as mean SD values. 3. Results and discussion 3.1. Acid catalyzed transesterication The effect of different process parameters such as reaction temperature, catalyst quantity, and reaction time on biodiesel yield was evaluated and presented below. 3.1.1. Effect of reaction temperature Effect of temperature on the yield of biodiesel is shown in Figs. 1 3. At different levels of catalyst quantity, highest yield (99.01 0.71%) of biodiesel was obtained at 50 C in case of chicken tallow. The production of biodiesel from mutton tallow also showed a similar behavior but its yield increased with temperature and was higher (93.21 5.07%.) at 60 C. The requirement of different temperatures for maximum yield of biodiesel from chicken tallow and mutton tallow was due to difference in their fatty acid composition as shown in Table 1. Mutton tallow contained more percentage of saturated fatty acid than unsaturated ones, so it needed higher reaction temperature in comparison to chicken tallow for maximum yield of biodiesel. Temperatures greater than 60 C, were not used for biodiesel production because at higher temperatures H2SO4

120

Biodiesel Yield (wt. %)

100 80 60 40 20 0 25 30

Chicken fat

Mutton fat

35

40

45

50

55

60

65

Temperature (C)
Fig. 1. Effect of temperature on the yield of biodiesel produced from chicken and mutton fats at 1.25 g catalyst.

H.N. Bhatti et al. / Fuel 87 (2008) 29612966

120
60

2963

Biodiesel Yield (wt. %)

Biodiesel Yield (wt. %)

100

Chicken fat

Mutton fat

50 40 30 20 10 0
Chicken fat Mutton fat

80

60

40

20

Catalyst (g)
0 25 30 35 40 45 50 55 60 65

Temperature (C)
Fig. 2. Effect of temperature on the yield of biodiesel produced from chicken and mutton fats at 2.5 g catalyst.

Fig. 4. Effect of catalyst on the yield of biodiesel produced from chicken and mutton fats at 30 C.

100
Chicken fat Mutton fat

90

Biodiesel Yield (wt. %)

120

80 70 60 50 40 30 20 10

Biodiesel Yield (wt. %)

100

Chicken fat

Mutton fat

80

60

40

0 0 1 2 3 4 5 6

20

Catalyst (g)
Fig. 5. Effect of catalyst on the yield of biodiesel produced from chicken and mutton fats at 40 C.
25 30 35 40 45 50 55 60 65

Temperature (C)
Fig. 3. Effect of temperature on the yield of biodiesel produced from chicken and mutton fats at 5 g catalyst.
120
Chicken fat Mutton fat

Table 1 Fatty acid prole of biodiesel produced from chicken and mutton fats Fatty acid (%) Caprylic acid Capric acid Lauric acid Tridecnoic acid Myristic acid Myristoleic acid Palmitic acid Palmitoleic acid Heptadecanoic acid Stearic acid Oleic acid Linoleic acid Linolenic acid Arachidic acid Ecosenoic acid Behenic acid Chicken fat 0.0144 0.0285 0.7901 0.2465 0.2286 0.0827 24.654 6.9231 0.1419 6.2515 45.1812 12.5832 0.3832 0.0992 0.5863 0.0952 Mutton fat 0.4928 0.3703 4.3854 0.1558 0.7879 0.4355 28.1036 0.4226 0.1387 27.1957 31.2798 1.5957 0.8831 0.6075 0.4008 ND

Biodiesel Yield (wt. %)

100

80

60

40

20

0 0 1 2 3 4 5 6

Catalyst (g)
Fig. 6. Effect of catalyst on the yield of biodiesel produced from chicken and mutton fats at 50 C.

could burn sum of oil which cause low yield of biodiesel [18]. Shimada et al. [21] and Kse et al. [22] conducted the methanolysis of vegetable oil and observed that the optimal reaction temperature for biodiesel production varied from 50 to 60 C. 3.1.2. Effect of catalyst The dependence of biodiesel yield on H2SO4 amount was studied at four different temperatures (3060 C) with an increment of

10 C (Figs. 47). The yield of biodiesel was found to be highly dependent on the amount of catalyst. In case of both chicken and mutton tallow biodiesel yield, increased with increase in H2SO4 quantity from 1 to 3 g and further increase in catalyst quantity resulted in decrease in the biodiesel yield at 30, 40 and 60 C. Interestingly a different trend was observed at 50 C. At this temperature, the yield of biodiesel was found inversely related to catalyst quantity. Similar results have also been reported earlier [2327]. The results clearly demonstrated that the most suitable catalyst quantity for biodiesel production was 1.25 and 2.5 g (on tallow

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120
Chicken fat Mutton fat

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Biodiesel Yield (wt. %)

100

80

60

tained results, it can be concluded that suitable reaction time for chicken and mutton fats was 24 h. The results of present study clearly demonstrated that the conversion rate increases with reaction time [3031]. Ma et al. [32], on studying beef tallow transesterication using methanol, found that reaction was very slow during the rst few minutes due to mixing and dispersion of methanol as in the present study. They also observed that the yield of biodiesel increased with time. 3.2. Base catalyzed transesterication Methanolysis of chicken and mutton tallow was carried out using KOH as a catalyst via three different reaction methods. Method 1 was optimum in the reaction with the % yield of 88.14 1.12 and 78.33 1.23 for chicken and mutton tallow, respectively at 30 1 C (Fig. 9). Alkaline alcoholysis of chicken and mutton tallow was performed well below the boiling point of methanol to accelerate the saponication of glycerides by the base catalyst before completion of the alcoholysis [3335]. The results of present study are in accordance with studies of Dorado et al. [33] and Meher et al. [36] who reported that after certain limit, increase in the concentration of catalyst, there was a decrease in the yield of methyl esters due to formation soap in the presence of high amounts of catalyst, which increased the viscosity of the reactants and lowered the yield. This was the main reason for the low yield in case of method 2. The results clearly demonstrated that acid catalyzed reaction was more suitable for biodiesel production in comparison to base catalyzed one. Other researchers have also noted that methanol to oil molar ratio, reaction temperature, reaction time and catalyst quantity play important role in production of biodiesel using methanolysis [3740]. 3.3. Quantication of methyl esters Gas chromatographic analyses were carried out for the quantication of biodiesel produced (Table 1). From the obtained results it can be concluded that mutton fat has higher percentage of saturated fatty acids and lower percentage of unsaturated fatty acid in comparison to chicken fat. Oleic acid (C18:1) was the major fatty acid in both fats (45.18% and 31.27% in chicken and mutton fats, respectively), palmitic acid (16:0) which was 24.65% and 28.10% in chicken and mutton fats, respectively. A total of 98.29% and 97.25% fatty acids were identied in chicken and mutton fats,

40

20

0 0 1 2 3 4 5 6

Catalyst (g)
Fig. 7. Effect of catalyst on the yield of biodiesel produced from chicken and mutton fats at 60 C.

weight basis) at 50 C and 60 C for chicken and mutton tallow, respectively. This was so because at higher temperatures, higher concentrations of H2SO4 could burn some of oil, which caused low yield of biodiesel product [28]. The yield of biodiesel under optimized conditions was 99.01 0.71% and 93.21 5.07% in case of chicken tallow and mutton tallow, respectively. These results can be explained from the viewpoint of the reversible nature of the transesterication process as explained by Darnoko [29]. Freedman et al. [30] found that although alkali, acid, or enzyme catalyst can be used for the production of biodiesel, however, if a glyceride has a higher free fatty acid content and more water, acid catalyzed transesterication is more suitable. 3.1.3. Effect of reaction time The effect of reaction time on the yield of biodiesel was studied at different time intervals ranging from 0.75 to 24 h at constant temperature and catalyst quantity (1.25 g at 50 C for chicken tallow and 2.5 g at 60 C mutton tallow (Fig. 8). Tallow (5 g) was thoroughly mixed by constant shaking (130 rpm) with 150 mL of methanol and 1.25 g of concentrated H2SO4 for chicken tallow and 2.5 g of concentrated H2SO4 for mutton tallow for a time interval varied from 0.75 to 24 h. The % yield of biodiesel was directly proportional to reaction time in both cases. Thus, from the ob-

120
Chicken fat Mutton fat

100
Chicken fat Muttonfat

90 80

100

Biodiesel Yield (wt. %)

Biodiesel Yield (wt.%)

70 60 50 40 30 20

80

60

40

20
10

0 0 5 10 15 20 25 30

0 Ireland Method1 IrelandMethod 2 Method 3 (Peterson etal.,)

Time (h)
Fig. 8. Effect of shaking time on the yield of biodiesel produced from chicken and mutton fats at constant temperature and catalyst quantity.

Base Catalysed Methods

Fig. 9. Effect of different base catalyzed methods on the yield of biodiesel produced from chicken and mutton fats.

H.N. Bhatti et al. / Fuel 87 (2008) 29612966 Table 2 Fuel properties of biodiesel produced from chicken and mutton fats Properties Density Viscosity Cloud point Pour point Moisture contents Ash contents Acid value Iodine value Saponication value Cetane value Units kg/l kg/m s C C w/w% w/w% mg KOH/g gI2/100 g mg KOH/g Biodiesel from chicken fat 0.867 0.00625 5 6 0.01 0.022 0.25 130 251.23 61.0 Biodiesel from mutton fat 0.856 0.00598 4 5 0.02 0.025 0.65 126 244.50 59.0 Biodiesel from waste cooking oil Ref. [41] 0.890 1 0.015 0.48 54.5 Biodiesel standards 0.860.9 <0.005 <0.05 <0.02 <0.8 <120 <312.5 58

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Test methods ISO 3675 ISO 3104 ISO 3015 ISO 3016 ISO 662 ISO 6884 ISO 660 ISO 3961 ISO 3657 EN ISO 5165

respectively. Both fats were found highly suitable to produce biodiesel with recommended fuel properties. Gerpan et al. [20] also reported that fats or oils containing fatty acids having carbon atom more than 15, produced biodiesel of superior quality. 3.4. Characteristics of biodiesel from chicken and mutton fats The fuel properties of biodiesel such as density, viscosity, ash point, cloud point, pour point, acid value, iodine value and saponication number were determined and are reported in Table 2. The physical and fuel properties of biodiesel from chicken and mutton fats in general were comparable to those of recommended properties. Meng et al. [41] found similar results while studying the biodiesel production from waste cooking oil. The results suggested that the new process, with combined bioengineering and transesterication, could be a feasible and effective method for the production of high quality biodiesel from chicken and mutton fats. The biodiesel from these fats could be a competitive alternative to conventional diesel fuel. 4. Conclusions Biodiesel produced from chicken and mutton fats using acid catalysis resulted in higher yield in comparison to base catalysis. Different experimental parameters such as amount of catalyst, temperature and time affected the production of biodiesel. Optimum amount of H2SO4, temperature and time were 1.25 g (on fat weight basis), 50 C and 24 h for chicken fat, and 2.5 g (on fat weight basis), 60 C and 24 h for mutton fat. Results of present study clearly demonstrated that the use of chicken and mutton fats is very suitable as low cost feed stocks for biodiesel production. Acknowledgment The authors are thankful and greatly acknowledge the technical support from Director, Ayub Agricultural Research Institute (AARI), Faisalabad, Pakistan. References
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